EP0174135B2 - Heat-developable color light-sensitive material - Google Patents

Heat-developable color light-sensitive material Download PDF

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Publication number
EP0174135B2
EP0174135B2 EP85305952A EP85305952A EP0174135B2 EP 0174135 B2 EP0174135 B2 EP 0174135B2 EP 85305952 A EP85305952 A EP 85305952A EP 85305952 A EP85305952 A EP 85305952A EP 0174135 B2 EP0174135 B2 EP 0174135B2
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EP
European Patent Office
Prior art keywords
silver
group
dye
light
sensitive
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EP85305952A
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German (de)
English (en)
French (fr)
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EP0174135A2 (en
EP0174135A3 (en
EP0174135B1 (en
Inventor
Tawara Komamura
Masaru Iwagaki
Toyoaki Masukawa
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Konica Minolta Inc
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Konica Minolta Inc
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Publication of EP0174135B1 publication Critical patent/EP0174135B1/en
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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • G03C8/40—Development by heat ; Photo-thermographic processes
    • G03C8/4013—Development by heat ; Photo-thermographic processes using photothermographic silver salt systems, e.g. dry silver
    • G03C8/408—Additives or processing agents not provided for in groups G03C8/402 - G03C8/4046
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
    • G03C1/498—Photothermographic systems, e.g. dry silver
    • G03C1/49836—Additives
    • G03C1/49863—Inert additives, e.g. surfactants, binders
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • G03C8/40—Development by heat ; Photo-thermographic processes
    • G03C8/4013—Development by heat ; Photo-thermographic processes using photothermographic silver salt systems, e.g. dry silver
    • G03C8/4033—Transferable dyes or precursors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/165—Thermal imaging composition

Definitions

  • the present invention relates to a heat-developable color light-sensitive material, and more particularly to such a material whose transfer image has a high maximum density with little fog and excellent color separability.
  • the color photographic process which uses a conventional light-sensitive silver halide is superior in e.g. light sensitivity, gradation, image preservability, to other color photographic processes, and has been most extensively used to date.
  • this process has many disadvantages.Because development, bleaching, fixing and washing are all wet processes the time and labor costs are large, the processing chemicals can harm the human body and pollute the processing room, and disposal of the waste liquids is laborious and costly.
  • Heat-developable black-and-white light-sensitive materials whose development is effected by heating, are known and described in, for example JP-B- Nos 4921/1968 and 4924/1968 disclosing those light-sensitive materials comprising organic silver salts, silver halides and developing agents.
  • Various heat-developable color light-sensitive materials developed on the basis of such heat-developable black-and-white light-sensitive materials are also known.
  • JP-A- Nos.179840/1982 corresponding to US ⁇ A ⁇ ,463,079), 186744/1982 (US ⁇ A ⁇ 4,474,867), 198458/1982 (EP-A-66,282), 207250/1982 (EP ⁇ A ⁇ 67,455), 40551/1983 (US ⁇ A ⁇ 4,430,415), and 58543/1983 (EP-A-76,482), and disclosed also in our applications JP-A-Nos. 12431/1984 and 229649/1982.
  • EP-A-0123916 which forms part of the state of the art by virtue of Article 54(3), discloses, in Example 2, a heat-developable colour photographic material comprising a light-sensitive mixed crystal silver haloiodide having a silver iodide content of 4 to 40 mole % and layers comprising an organic silver salt, a reducing agent, and a yellow, magenta or cyan dye donator substance using gelatin as binder in an amount of 6.2 g/m 2 of the various layers.
  • the color light-sensitive material in order to obtain a multicolor image on the image-receiving layer by the diffusion transferof dyes by heating without requiring wet processing, advantageously has a multi-layer construction similar to that of conventional color light-sensitive materials.
  • a blue-sensitive layer containing a yellow coupler In the case of a photographic paper, usually in order from the bottom layer, it typically comprises a blue- sensitive layer containing a yellow coupler, a green-sensitive layer containing a magenta coupler, and a red-sensitive layer containing a cyan coupler.
  • the layers are generally a cyan dye-donating red-sensitive layer, then a magenta dye-donating green-sensitive layer, and then an uppermost yellow dye-donating blue-sensitive layer.
  • interlayers to prevent the colors from mixing are provided between the layers, and in most cases a yellow filter layer is provided between the blue-sensitive layer and the green-sensitive layer.
  • the light-sensitive material has the disadvantages that, due to its undesirable multilayer construction, the fog of, particularly, the lower layer, i.e. the layer located furthest from the image-receiving layer, increases as compared to the case of a single layer material, and its color separability is inadequate. Thus, an improvement in this situation has been much sought after.
  • the present invention seeks to provide a multilayer heat-developable color light-sensitive material which has a high maximum density, low fog, excellent color separability and which has excellent diffusion transferability of the dye from the bottom layer.
  • the present invention provides a heat-developable color light-sensitive material suitable for diffusion transfer comprising a support having thereon a plurality of layers comprising a layer comprising light-sensitive silver halide grains, an organic silver salt, a reducing agent, a yellow dye donator substance and a binder, a layer comprising light-sensitive silver halide grains, an organic silver salt, a reducing agent, a magenta dye donator substance and a binder, and a layer comprising light-sensitive silver halide grains, an organic silver salt, a reducing agent, a cyan dye donator substnace and a binder, the total amount of binder in said layers being from 3 g to 10 g per m 2 of said support, said binder being a mixture of gelatin and polyvinyl pyrrolidone and polyvinyl alcohol.
  • the multi-layer heat-developable color light-sensitive material of the invention which comprises binder in an amount of from 3 g to 10 g per m 2 of the support is capable of producing a transfer image having not only a high density with little fog but also excellent color separability, and further, by the incorporation into the material of an appropriate amount of a heat solvent it becomes capable of producing an image which has excellent transferabil ity.
  • the heat-developable color light-sensitive material is of a multi-layer construction as stated above, and the total quantity of the binder used in the light-sensitive layers is from 3 grams to 10 grams per sq. meter of the support.
  • the quantities of the non-binder constituents retained by the binder such as, for example, a silver halide, organic silver salt, reducing agent and dye donator, become smaller than the required quantities, and as a result, the image produced is not of sufficient maximum density, or alternatively, the retention of the above constituents by the binder becomes inadequate, thus sometimes causing an undesirable diffusion (mainly of the dye donator) between the layers making the resulting color turbid.
  • the quantity of the binder exceeds the upper limit of the range, the maximum density decreases, while the minimum density increases, which are undesirable phenomena.
  • a hydrophilic binder is used as such binder.
  • the transfer efficiency of the dye is improved to increase the maximum density and no color turbidity is caused by diffusion of e.g. the dye donator between the layers.
  • the polyvinyl alcohols preferably used are those whose saponification degree is more than 75%. If necessary, a mixture of two or more different binders may be used.
  • the gelatin content in the binder is preferably more than 20% by weight, and more preferably from 20 to 80% by weight, and the total amount of the gelatin should preferably be from 0.6 to 5 g per m 2 of the support.
  • gelatin is effective in retaining the dye donator in the layer during its development as well as in restraining fog, and the above effects are particularly significant when the gelatin content of the binder is more than 20% by weight, and the transferability of the dye becomes particularly good and the maximum density becomes high when the content is less than 80% by weight (preferably less than 60% by weight).
  • the heat solvent is a material that is solid, semi-solid or liquid at normal temperature and upon being heated dissolves, fuses or plasticizes the binder.
  • the preferred examples of it include e.g. urea derivatives, amide derivatives, polyethylene glycols and polyhydric alcohols. These heat solvents may be used either alone or in combination.
  • the preferred heat solvents are those capable of improving not only the transferability of the dye but also the developability and releasability or formability of the dye.
  • the heat solvent need not have a melting point less than the heat-developing temperature and may be liquid at normal temperature.
  • the preferred urea derivatives are those of Formula (1): wherein X is an oxygen atom or a sulfur atom; and R 1 , R 2 , R 3 and R 4 , which may be the same or different, are each hydrogen, a substituted or unsubstituted alkyl group (the R 1 -R 2 and R 3 ⁇ R 4 pairs may each combine to form a cyclic ring) having not more than 12 carbon atoms, or a substituted or unsubstituted aryl group having not more than 12 carbon atoms.
  • the preferred amide derivatives are those of Formula (2): wherein R 5 is a substituted or unsubstituted alkyl group having not more than 12 carbon atoms or a substituted or unsubstituted aryl group having not more than 12 carbon atoms; and R 6 and R 7 which may be the same or different are each hydrogen, a substituted or unsubstituted alkyl group having not more than 6 carbon atoms, a substituted or unsubstituted aryl group having not more than 12 carbon atoms or a substituted or unsubstituted acyl group having not more than 6 carbon atoms, or R 5 and R 6 may combine with each other to form a cyclic ring.
  • the preferred polyethylene glycols are those whose molecular weight is from 150 to 10,000.
  • the preferred polyhydric alcohols are those having not more than 12 carbon atoms in total, and are cyclic or chain alcohols having from 2 to 6 hydroxy groups (allowed to be substituted with e. g. a halogen atom, an alkoxy group or an acyl group).
  • urea derivatives examples include urea, thiourea, 1,3-dimethyl-urea, 1,3-diethyl-urea, diethylene urea, 1,3-diisopropyl-urea, 1,3-dibutyl-urea, 1,1-dimethyl-urea, 1,3-dimethoxyethyl-urea, 1,3-dimethyl-thiourea, 1,3-dibutyl-thiourea, tetramethyl thiourea, phenyl urea, tetramethyl urea and tetraethyl urea.
  • amide derivatives examples include acetamide, propionamide, n-butylamide, i-butylamide, benzamide, diacetamide, dimethylformamide, acetanilide, ethylacetamide acetate, 2-chloropropionamide, 3-chloropropionamide, phthalimide, succinic acid amide and N,N-dimethylacetamide.
  • polyhydric alcohols examples include 1 ,5-pentanediol, 1 ,6-hexane-diol, dixylitol, pentaerythritol, 1,4-cyclohexane-diol, 2,2-dihydroxybenzophenone, 1,8-octanediol and petriol (3-methylpentane-1,3,5-triol).
  • the heat solvent content is advantageously from 10% to 300% of the quantity of the binder, and preferably from 20% to 150%, and particularly preferably from 1 to 9 grams per m 2 of the support.
  • the heat solvents to be used may be used alone or in combination of two or more of them.
  • the heat-developable color light-sensitive material contains in the component layers thereof a yellow dye donator, a magenta dye donator and a cyan dye donator.
  • These dye donators are ones that release dyes (coupling dye-releasing type) or form dyes (coupling dye-forming type) by the coupling reaction thereof with the oxidation product of a developing agent, and they also include those dye donators which themselves are reductive (reducing dye donator) or oxidative (oxidizing dye donator), which release dyes by the reduction reaction or oxidation reaction thereof.
  • the preferred dye donators of the abovementioned coupling dye-releasing type are those compounds of formula (3): wherein C P1 represents a coupler residue after the hydrogen atom in the active position is eliminated; X represents a divalent linkage group or merely a double bond; and Dye is a diffusible dye residue.
  • the coupler residue represented by the above C P1 includes those of Formulae (4) to (9): wherein R i , R 2 , R 3 and R 4 are each e.g. hydrogen, halogen (preferably chlorine, bromine or iodine), a substituted or unsubstituted alkyl group (preferably an alkyl group having from 1 to 24 carbon atoms, such as methyl, ethyl, butyl, t-octyl, n-dodecyl, n-pentadecyl or cyclohexyl, or an aralkyl (such as phenyl-substituted alkyl group including a benzyl or phenthyl group) a substituted or unsubstituted aryl group (such as phenyl, naphthyl, tolyl, mesityl), an acyl group (such as acetyl, tetradecanoyl, pivaloyl,
  • a halogen preferably chlorine, bromine or iodine
  • an alkyl group preferably an alkyl group having from 1 to 2 carbon atoms, such as methyl or ethyl
  • a substituted or unsubstituted alkylamido group such as laurylamido
  • a substitutable phenoxyalkylamido group such as an alkyl-substituted phenoxyacetamido
  • a substituted or unsubstituted arylamido group such as benzoylamido
  • R 9 represents e.g.
  • R 10 is a substituted or unsubstituted arylamino group (such as anilino or anilino substituted with a halogen atom or an alkyl, alkoxy, alkylamino, arylamido or imido group); and R 11 , R 12 , R 13 , R 14 , R 15 and R 16 are each as defined in the foregoing R 1 and R 2 .
  • each of at least one of the R 1 through R 4 , at least one of the R 5 through R 8 ,at least one of R 9 and R 10 , at least one of R 11 and R 12 , at least one of R 13 , and R 14 , and at least one of R 15 and R 16 is a group substituted with a hydrophilic group or groups such as sulfo group or carboxy group.
  • the divalent linkage group represented by X includes
  • the dye residue represented by the Dye includes azo-type, azomethine-type, indoaniline-type, anthraquinone-type dye residues, and of these dye residues those having a molecular weight of not more than 600 are preferred.
  • the preferred coupling dye-forming type dye donators are those of Formula (10): wherein C P2 represents a coupler residue after eliminating the hydrogen atom in the active position; and Y represents a group which can split off from the coupler during the coupling reaction and which has a group containing at least a hydrophilic group such as a sulfo or carboxy group or these groups, and particularly preferably a group or polymer-chain residue having a straight-chain or branched-chain alkyl group, whose total number of carbon atoms is not less than 8.
  • the coupler residue represented by C P2 includes, e.g. , those having the following Formulas (11) through (15).
  • the particularly preferred coupler residues are those whose molecular weight is not more than 400 and which are substituted with a hydrophilic group such as a sulfo or carboxy group.
  • R 17 , R 18 , R 19 and R 20 are as defined in the R 1 , R 2 , R 3 , and R 4 of the foregoing Formula (4);
  • R 21 is as defined in the R 5 of Formula (5);
  • R 22 , R 23 and R 24 are as defined in the R 6 , R 7 and R 8 of Formula (5);
  • R 25 is as defined in the R 9 of Formula (6);
  • R 26 is as defined in the R 10 of Formula (6); and
  • R 27 , R 28 , R 29 and R 30 are as defined in the R 1 and R 2 of Formula (4).
  • the foregoing reducing dye donator includes those compounds of Formula (16): wherein Z is a reducing substrate that can be oxidized by an organic silver salt; and Dye is a dye residue Exam- pies of the dye donator of this type are described in, e.g., JP ⁇ A ⁇ 179840/1982 (corresponding to US ⁇ A ⁇ 4,463,077).
  • the particularly preferred ones among these dye donators are those of the coupling dye-forming type.
  • magenta dye donator The following are typical examples of the magenta dye donator:
  • the quantity of the dye donator used is typically from 0.01 to 10 moles per mole of the organic silvan salt used, and preferably from 0.1 to 2.0 moles.
  • the dye donator is used by being incorporated into heat-developable light-sensitive layers or other photographic component layers.
  • the dye donator may be dissolved in a high-boiling solvent as described in US ⁇ A ⁇ 2,322,027 as a method for dispersing couplers.
  • a low-boiling solvent may also be used in combination with the high-boiling solvent to dissolve the dye donator to be incorporated into the heat-developable light-sensitive layer.
  • solvents known as the high-boiling solvent include, e.g., di-n-butyl phthalate, tricresyl phosphate, dioctyl phthalate and n-nonyl-phenol, and those known as the low-boiling solvent include, e.g., methyl acetate, butyl propionate, cyclohexanol and diethylene-glycol monolaurate. These solvents may be used alone or in a mixture.
  • the dye donator thus dissolved in such solvents may be mixed with an aqueous solution containing a hydrophilic binder material such as gelatin containing an anionic surface active agent such as an alkylbenzenesulfonic acid or alkylnaphthalenesulfonic acid, and/or a nonionic surface active agent such as a sorbitan- monolaurate, and the mixture may be emulsifiedly dispersed by means of a colloid mill or ultrasonic disperser to be incorporated into the heat-developable light-sensitive layer.
  • a hydrophilic binder material such as gelatin containing an anionic surface active agent such as an alkylbenzenesulfonic acid or alkylnaphthalenesulfonic acid, and/or a nonionic surface active agent such as a sorbitan- monolaurate
  • the above-mentioned high-boiling solvent is used in a quantity necessary for completely dissolving the dye donator; the quantity is preferably from 0.05 to 100 parts per part of the dye donator.
  • Fischer's dispersion is another method for dispersion called “Fischer's dispersion” as a preferred dispersion method other than the above method.
  • the Fischer's dispersion is such that a dye donator having both hydrophilic and hydrophobic components in the same molecule is dissolved into an aqueous alkaline solution to be dispersed.
  • an organic solvent having compatibility with water may be added, or the dye donator may be heated or stirred (by means of a homogenizer or ultrasonic disperser), or this process may be effected with the aid of a surface active agent.
  • the alkali agent for such an aqueous alkaline solution may be an inorganic base or organic base compatible with water.
  • the mixture may, if necessary, be subjected to pH control.
  • pH control an organic or inorganic acid compatible with water may be used.
  • anionic or nonionic surface active agents may be used, and of these agents anionic surface active agents are most suitably used.
  • Fischer's dispersion is sometimes called “Agfa dispersion", for which reference can be made to the details described in GB-A-45,555, GB-A-465,823 and GB-A-29,897.
  • the heat-developable light-sensitive layer contains a light-sensitive silver halide along with the foregoing dye donator.
  • the light-sensitive silver halide which may be used includes silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, silver chloroiodobromide, and a mixture of these halides.
  • the light-sensitive silver halide emulsion may be prepared by any one of such methods as the single-jet method or double-jet method, which are known to those skilled in the art, but in this invention the light-sensitive silver halide will give better results when prepared in the usual manner.
  • the light-sensitive silver halide emulsion may be chemically sensitized by any one of those methods well-known in the photographic field.
  • the sensitizing methods include e.g. gold sensitization, sulfur sensitization, gold-sulfur sensitization and reduction sensitization.
  • the silver halide of the above emulsion may be coarse-grained or fine-grained, but the preferred particle size of the silver halide should be from about 1.5 ⁇ m to about 0.001 ⁇ m, and more preferably from about 0.5 ⁇ m to about 0.01 ⁇ m.
  • the above-prepared light-sensitive silver halide emulsion can be most suitably applied to the heat-developable light-sensitive layer, the component layer of the light-sensitive material of this invention.
  • the light-sensitive silver salt-forming component for use in this preparation includes inorganic halides such as those halides represented by MXn (wherein M represents hydrogen, an NH 4 group or a metallic atom; X represents CI, Br or I; and n is I when the M is hydrogen or an NH 4 group, and, when the M is a metallic atom, is the valence thereof, the metallic atom including e.g.
  • halogen containing metallic complexes such as K 2 PtC1 6 , K s PtBr s , HAuC1 4 , (NH 4 ) 2 IrCl 6 , (NH 4 ) 3 IrCl 6 , (NH 4 ) 2 RuCl 6 , (NH 4 ) 3 RuCl 6 , (NH 4 ) 3 RhC1 6 or (NH 4 ) 3 RhBr 6 ), onium halogen containing metallic complexes (such as K 2 PtC1 6 , K s PtBr s , HAuC1 4 , (NH 4 ) 2 IrCl 6 , (NH 4 ) 3 IrCl 6 , (NH 4 ) 2 RuCl 6 , (NH 4 ) 3 RuCl 6 , (NH 4 ) 3 RhC1 6 or (NH 4 ) 3 RhBr 6 ), onium hal
  • light-sensitive silver halide and light-sensitive silver halide salt-forming components may be used in combination in various ways, and the amount used generally is from 0.001 mole to 5.0 moles per mole of the organic silver salt, and preferably from 0.01 mole to 2.0 moles.
  • the light-sensitive silver halide used in this invention differs in the color sensitivity according to the respective layers.
  • a blue-sensitive silver halide is used for the layer containing a yellow dye donator
  • a green-sensitive silver halide is used for the layer containing a magenta dye donator
  • a red-sensitive silver halide is used for the layer containing a cyan dye donator.
  • the above combinations are not necessarily imperative, depending on the exposure method used, and other embodiments may also be applied.
  • the blue-sensitive silver halide, green-sensitive silver halide and red-sensitive silver halide emulsions used in this invention can be obtained by adding appropriate spectrally-sensitizing dyes to the foregoing silver halide emulsion.
  • Typical spectrally-sensitising dyes used in this invention include, e.g., cyanines, merocyanines, conplex (3- or4-nucieus) cyanines, holopolacyanines, styryls, and hemicyanines and oxonols.
  • cyanine dyes the preferred ones are those having a basic nucleus such as thiazoline, oxazoline, pyrroline, pyridine, oxazole, thiazole, selenazole or imidazole.
  • nuclei may have an alkyl, alkylene, hydroxylalkyl, sulfoalkyl, carboxyalkyl or aminoalkyl group, or an enamine group capable of forming a condensed carbocyclic or heterocyclic ring, and may also be of the symmetrical or asymmetrical form, and further the methine chain or polymethine chain thereof may have an alkyl, phenyl, enamine or heterocyclic substituent.
  • Merocyanine dyes may have an acid nucleus such as, e.g., thiohydantoin nucleus, rhodanine nucleus, oxazolidinedione nucleus, thiazolidinedione nucleus, barbituric acid nucleus, thiazolinethione nucleus, malononitrile nucleus or pyrazolone nucleus, in addition to the above-mentioned basic nuclei.
  • These acid nuclei may have a further substituent such as an alkyl, alkylene, phenyl, carboxylalkyl, sulfoalkyl, hydroxyalkyl, alkoxyalkyl, alkylamine or heterocyclic group.
  • these dyes may be used in combination. Further these dyes may be used in combination with supersensitizing additives which absorb no visible rays such as ascorbic acid derivatives, azaindene cadmium salts, organic sulfonic acids, as described in US-A-2 933 390 and US-A-2,937,089.
  • supersensitizing additives which absorb no visible rays such as ascorbic acid derivatives, azaindene cadmium salts, organic sulfonic acids, as described in US-A-2 933 390 and US-A-2,937,089.
  • the quantity of these dyes added is from 1 x 10-4 to 1 mole per mole of the silver halide or silver halide- forming component, and preferably from 1 x 10- 4 to 1 x 10- 1 mole.
  • the organic silver salt used for the heat-developable color light-sensitive material includes aliphatic carboxylic acid silver salts such as silver laurate, silver myristate, silver palmitate, silver stearate, silver arachido- nate and silver behenate; aromatic carboxylic acid silver salts such as silver benzoate and silver phthalate; amino group-having silver salts such as silver benzotriazole, silver saccharine, silver phthalazinone and silver phthalimide; silver salts of mercapto group- or thione group-having compounds such as silver 2-mercaptoben- zoxazole, silver mercaptoxadiazole, silver mercaptobenzothiazole, silver 2-mercaptobenzoimidazole, silver 3-mercaptophenyl-1,2,4-triazole; and other silver compounds such as silver 4-hydroxy-6-methyl- 1,3,3a, 7-tetrazaindene and silver 5-methyl-7-hydroxy-1,2,3,4,6-pentazaindene
  • those silver compounds as described in U.S. Research Disclosure Nos. 16966 and 16907; and GB ⁇ A ⁇ 1,590,956 and GB ⁇ A ⁇ 1,590;957 may also be used.
  • those imino group-having silver salts such as, for example, benzotriazole silver salts are preferred which include alkyl-substituted silver benzotriazoles such as silvermethylbenzotriazole, halogen-substituted silver benzotriazoles such as silver bromoben- zotriazole, amido-substituted silver benzotriazoles such as silver 5-acetamidobenzotriazole, and those compounds as described in GB ⁇ A ⁇ 1,590,956 and GB ⁇ A ⁇ 1,590,957 including, e.g., silver N-[6-chloro-4-N(3,5-dichloro-4-hydroxyphenyl)-imino-l-oxo-5-methyl-2,5-cyclo
  • nitrobenzotriazoles of Formula (16) and those benzotriazoles of Formula (17) may also be advantageously used: wherein R 32 is a nitro group; R 33 and R34 may be either the same as or different from each other and each is a halogen atom (such as chlorine, bromine or iodine), a hydroxy group, a sulfo group or a salt thereof (such as sodium salt, potassium salt or ammonium salt) a carboxy group or a salt thereof (such as sodium salt, potassium salt or ammonium salt), a nitro group, a cyano group, or a substitutable carbamoyl or sulfamoyl group, a substitutable alkyl group (such as methyl, ethyl or propyl), a substitutable alkoxy group (such as methoxy or ethoxy), a substitutable aryl group (such as phenyl) or a substitutable amino group; m is 0, 1 or 2; and n is zero
  • the substituent to the above-mentioned substitutable carbamoyl group includes, e.g., methyl group, ethyl group or acetyl group, that to the above substitutable sulfamoyl group includes, e.g., methyl group, ethyl group or acetyl group; that to the above substitutable alkyl group includes, e.g.carboxy group or ethoxycarbonyl group; that to the above substitutable aryl group includes, e.g. sulfo group or nitro group; that to the above substitutable alkoxy group includes, e. g. carboxy group or ethoxycarbonyl group; and that to the above substitutable amino group includes, e.g., acetyl group, methanesulfonyl group or hydroxy group.
  • Those compounds have Formula (16) are silver salts of benzotriazole derivatives having at least one nitro group, examples of which include the following compounds: silver 4-nitrobenzotriazole, silver 5-nitrobenzotriazole, silver 5-nitro-6-chlorobenzotriazole, silver 5-nitro-6-methylbenzotriazole, silver 5-nitro-6-methoxybenzotriazole, silver 5-nitro-7-phenylbenzotriazole, silver 4-hydroxy-5-nitrobenzotriazole, silver 4-hydroxy-7-nitrobenzotriazole, silver 4-hydroxy-5,7-dinitrobenzotriazole, silver 4-hydroxy-5-nitro-6-chlorobenzotriazole, silver 4-hydroxy-5-nitro-6-methylbenzotriazole, silver 4-sulfo-6-nitrobenzotriazole, silver 4-carboxy-6-nitrobenzotriazole, silver 5-carboxy-6-nitrobenzotriazole, silver 4-carbamoyl-6-nitrobenzotriazole, silver 4-sulfamoyl-6-nitrobenzotriazo
  • R 35 is a hydroxy group, a sulfo group or a salt thereof (such as sodium salt, potassium salt or ammonium salt), a carboxy group or a salt thereof (such as sodium salt, potassium salt or ammonium salt), a substitutable carbamoyl group or a substitutable sulfamoyl group;
  • R 36 is a halogen (such as chlorine, bromine or iodine), a hydroxy group, a sulfo group or a salt thereof (such as sodium salt, potassium salt or ammonium salt), a carboxy group or a salt thereof (such as sodium salt, potassium salt or ammonium salt), a nitro group, a cyano group, or a substitutable alkyl group (such as methyl, ethyl or propyl), a substitutable aryl group (such as phenyl), a substitutable alkoxy group (such as methoxy or ethoxy) or a substitutable amino group;
  • p is 1
  • the substituent to the above-mentioned substitutable carbamoyl group represented by R 35 includes, e.g., methyl group, ethyl group and acetyl group; and that to the above substitutable sulfamoyl group includes, e.g., methyl group ethyl group and acetyl group.
  • the substituent to the above substitutable alkyl group includes, e.g.
  • carboxy group and ethoxycarbonyl group that to the above substitutable aryl group includes sulfo group and nitro group; that to the above substitutable alkoxy group includes, e.g., carboxy group and ethoxycarbonyl group; and that to the above substitutable amino group includes acetyl group, methanesulfonyl group and hydroxy group.
  • Examples of those organic silver salts having Formula (17) include the following compounds: silver 4-hydroxy-benzotriazole, silver 5-hydroxybenzotriazole, silver 4-sulfobenzotriazole, silver 5-sulfobenzotriazole, silver benzotriazole-sodium 4-sulfonate, silver benzotriazole-sodium 5-sulfonate, silver benzotriazole-potassium 4-sulfonate, silver benzotriazole-potassium 5-sulfonate, silver benzotriazole-ammonium 4-sulfonate, silver benzotriazole-ammonium 5-sulfonate, silver 4-carboxybenzotriazole, silver 5-carboxybenzotriazole, silver benzotriazole-sodium 4-carboxylate, silver benzotriazole-sodium 5-carboxylate, silver benzotriazole-potassium 4-carboxylate, silver benzotriazole-potassium 5-carboxylate, silver benzotriazole-
  • the quantity of the organic silver salt used is usually from 0.05 g to 10.0 g per m 2 of the support, and preferably from 0.2 g to 2.0 g.
  • the reducing agent to be used for the heat-developable color light-sensitive material includes those known color developing agents such as p-phenylene-diamine type and p-aminophenol-type developing agents, phos- phoroamidophenol-type and sulfonamidophenol-type developing agents, and hydrazone-type color developing agents, or precursors of these agents, as described in US-A-3,531,286, US-A-3,761,270 and US ⁇ A ⁇ 3,764,328; U.S. Research Disclosure Nos.
  • JP-A-27132/1981 and the most preferred are p-(N,N-dialkylaminophenyl)-sulfamine developing agents as described in JP ⁇ A ⁇ 146133/1981 and our Japanese Patent Application No 225928/1982.
  • the quantity of the reducing agent used is usually from 0.05 mole to 10 moles per mole of the organic silver salt, and preferably from 0.1 mole to 3 moles.
  • the heat-developable color light-sensitive material may, if necessary, contain various additives in addition to the above-described components.
  • additives usable as the development accelerator include those alkali-releasing agents as described in US-A- Nos. 3,220,840, 3,531,285, 4,012,260, 4,060,420, 4,088,496 and 4,207,392; and U.S. Research Disclosure Nos.
  • Substances usable as the toning agent include phthalazinone, phthalimide, pyrazolane, quinazoline, N-hydroxynaphthali- mide, benzoxazine, naphthoxazinedione, 2,3-dihydrophthalazinedione, 2,3-dihydro-1,3-oxazine-2,4-dione, oxypyridine, aminopyridine, hydroxyquinoline, aminoquinoline, isocarbstyryl, sulfonamide, 2H-1,3-benzothia- zine-2,4-(3H)-dione, benzotriazine, mercaptotriazole, dimercaptotetrazapentalene, phthalic acid, naphthalic acid and phthalamic acid, which are the compounds described in JP-A-Nos.
  • an antifoggant Usable as an antifoggant are those compounds as described in JP ⁇ B ⁇ 11113/1972; JP-A-Nos. 90118/1974, 10724/1974, 97613/1974, 101019/1975, 130720/1974, 123331/1975, 47419/1976, 57435/1976, 78227/1976, 104338/1976, 19825/1978, 20923/1978, 50725/1976, 3223/1976, 42529/1976, 81124/1976, 51821 / 1979 and 93149/1980; GB-A-1,455,271; US-A- Nos.
  • mercuric salts which include mercuric salts, oxidizing agents (such as N-halogenoace- tamide, N-halogenosuccinic acid imide, perchloric acid and perchlorates, inorganic peroxides and persulfates), acids and the salts thereof (such as sulfinic acid, lithium laurate, rosin, diterpenic acid and thiosulfonic acid), sulfur-containing compounds (such as mercapto compound-releasing compounds, thiouracil, disulfides, elemental sulfur, mercapto-1,2,4-triazole, thiazolinethione and polysulfide compounds), and other compounds such as oxazoline, 1,2,4-triazoles and phthalimide.
  • oxidizing agents such as N-halogenoace- tamide, N-halogenosuccinic acid imide, perchloric acid and perchlorates, inorganic peroxides and persulfates
  • hydrophilic benzotriazole derivatives such as 4-sulfobenzotriazole and 5-carboxybenzotriazole, and phenolic hydroxyl group-having oxidizing agents such as hydroquinone derivatives as described in Japanese Patent Application Nos. 66380/1984 and 56506/1984, are also useful as antifoggants.
  • hydrophilic benzotriazole derivative with the hydroquinone derivative further increases the antifogging effect.
  • a post-treatment anti-printout agent which includes those halogenated hydrocarbons such as tetrabromobutane, tribromoethane, 2-bromo-2-tolylacetamide, 2-bromo-2-tolylsulfonylacetamide, 2-tolylbromomethylsulfonylbenzothiazole and 2,4-bis(tribromomethyl)-6-methyl- triazine, as described in JP-A-Nos. 45228/1973, 119624/1975, 120328/1975, and 46020.
  • halogenated hydrocarbons such as tetrabromobutane, tribromoethane, 2-bromo-2-tolylacetamide, 2-bromo-2-tolylsulfonylacetamide, 2-tolylbromomethylsulfonylbenzothiazole and 2,4-bis(tribromomethyl)-6-methyl- triazine
  • sulfur containing compounds may be used for the post treatment.
  • sulfur containing compounds as described in JP-B-5393/1971; JP-A-Nos. 54329/1975 and 77034/1975, sulfur containing compounds may be used for the post treatment.
  • those isothiuronium-type stabilizer-precursors as described in US-A-Nos. 3,301,678, 3,506,444, 3,824,103 and 3,844,788 and those activator-stabilizer-precursors as described in US ⁇ A ⁇ Nos. 3,669,670, 4,012,260 and 4,060,420 may be contained in a liquid for the above treatment.
  • the heat-developable color light-sensitive material may, if necessary, be incorporated various additives such as spectrally sensitizing dyes, antihalation dyes, brightening agents, hardeners, antistatic agents, plasticizers and coating aids, in addition to the above described components.
  • various additives such as spectrally sensitizing dyes, antihalation dyes, brightening agents, hardeners, antistatic agents, plasticizers and coating aids, in addition to the above described components.
  • the foregoing light-sensitive silver halide, organic silver salt, reducing agent, dye donator and heat solvent which are the components of the heat-developable color light-sensitive material, may be contained either together in the same single layer or apart in two separate layers adjacent to each other.
  • the heat-developable color light-sensitive material in order to prevent possible occurrence of turbid color has, in addition to the above layers, interlayers between the respective different light-sensitive layers.
  • the above-mentioned interlayer may be a plain binder layer, and may also be a layer containing the same heat solvent, organic silver salt or reducing agent as those containing in the light-sensitive layer, and preferably contains a compound capable of scavenging the oxidized product of the reducing agent (hereinafter abridged to "Dp' scavenger").
  • the particularly preferred compound as the above Dp' scavenger is a coupler having an immobile group in the nonactive site substituent thereof.
  • the preferred group as the above immobile group is a group whose total number of carbon atoms is not less than 8 and/or a sulfo group, ahydrophilic group such as a hydroxy group, or a polymer residue.
  • the binder to be used as the foregoing interlayer is either a hydrophilic or hydrophobic binder, and it is particularly desirable that is the same binder as that used in the light-sensitive layer.
  • the layer containing the foregoing various components and other layers in this invention may be coated on any one of a variety of supports.
  • the support usable in this invention may be of any such materials as plastic films including cellulose-nitrate film, cellulose-esterfilm, polyvinyl-acetal film, polyethylene film, polyethylene- terephthalate film and polycarbonate film, glass plates, paper and metals such as aluminium.
  • photographic component layers such as an overcoat layer, subbing layer, backing layer or filter layers, may be provided.
  • the heat-developable color light-sensitive material of this invention is exposed imagewise and then heat-developed, whereby the heat-transferrable dye-imagewise distribution is formed from the foregoing dye donator, at least part of which imagewise distribution is then transferred onto an image receiving member having superposed relation with the light-sensitive material, thus forming a color image.
  • any of various transfer methods such as for example, the transfer which uses water or an organic solvent such as methanol, acetonitrile or dimethylformamide, or the heat transfer which uses a heat solvent or the heat-movable transfer by the sub- limaation of a dye itself, may be used.
  • the transfer which uses water or an organic solvent such as methanol, acetonitrile or dimethylformamide, or the heat transfer which uses a heat solvent or the heat-movable transfer by the sub- limaation of a dye itself, may be used.
  • the dye transfer can be effected by merely heating the light-sensitive material closely contacted with the image-receiving member.
  • the image-receiving member is enough if receptive of the dye thermally released or formed, but desirable to be formed of a mordant used in dye diffusion transfer-type light-sensitive materials, or a heat-resistant organic hig-molecular material whose glass transition temperature is in the range of from 40°C to 250°C, described in JP-A-207250/1982.
  • mordant examples include nitrogen-containing secondary or tertiary amines, nitrogen-containing heterocyclic compounds and quaternary cationic compounds thereof, those vinylpyridine polymers and vinyl-pyridine cationic polymers as disclosed in US-A-Nos 2,548,564, 2,484,430, 3,148,061 and 3,756,814, those dialkylamino group-containing polymers as disclosed in US-A-2,675,316, those aminoguanidine derivatives as disclosed in US-A-2,882,156, those mordants cross-linkable with e.g. gelatin, as disclosed in US-A-Nos.
  • the most useful mordants are those ammonium salt containing polymers as described in US-A-3,709,690.
  • a typical example of the ammonium salt containing polymers is polystyrene-co-N,N,N-tri-n-hexyl-N-vinyl-benzylammonium chloride.
  • the proportion of the styrene to the vinyl-benzylammonium chloride is typically from 1:4 to 4:1, and preferably 1:1.
  • the typical dye-diffusion-transfer image-receiving layer can be obtained by coating the ammonium salt- containing polymer mixed with gelatin on a support.
  • the transfer of the dye from the heat-developable light-sensitive layer onto the image-receiving layer may be made by use of a transfer solvent.
  • the transfer solvent includes low-boiling solvents such as methanol, ethyl acetate and diisobutyl ketone, and high-boiling solvents such as tri-n-cresyl phosphate and di-n-butyl phthalate.
  • a high-boiling solvent it may be emulsified by use of an appropriate emulsifier into gelatin to be incorporated into the image-receiving layer.
  • Examples of the foregoing heat-resistant organic high-molecular material include polystyrene having a molecular weight of from 2000 to 85000, polystyrene derivatives with a substituent having not more than 4 carbon atoms, polyvinylcyclohexane, polydivinyl-benzene, polyvinyl-pyrrolidone, polyvinyl-carbazole, polyallyl- benzene, polyvinyl alcohol, polyacetals such as polyvinyl formal or polyvinyl butyral, polyvinyl chloride, chlorinated polyethylene, polyethylene trichloride-fluoride, polyacrylonitrile, poly-N,N-dimethylallylamide, p-cyanophenyl group-containing, pentachlorophenyl group-containing and 2,4-dichlorophenyl group-containing polyacrylates, polyacryl chloroacrylate, polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate
  • a polycarbonate, polyanhydrides, polyamides, and cellulose acetates are useful.
  • These high-molecular materials may be used alone or in the form of copolymers in combination.
  • the particularly useful polymers include cellulose acetates such as triacetate or diacetate; polyamides in combination of heptamethylenediamine with terephthalic acid, of fluorenedipropylamine with adipic acid, of hexamethylenediamine with diphenic acid and of hexamethylenediamine with isophthalic acid; polyesters in combination of diethylene glycol with diphenyl-carboxylic acid and of bis-p-carboxyphenoxybutane with ethylene glycol; polyethylene terephthalate: polycarbonate, and polyvinyl chloride.
  • polymers may be ones reformed
  • a reforming agent such as cyclohexanedimethanol, isophthatic acid, methoxypolyethylene glycol or 1,2-di-carbomethoxy-4-benzenesulfonic acid, may also be useful.
  • any of the abovementioned polymers may be dissolved in an appropriate solvent, and the solution is coated over a support to form an image-receiving layer; or prepared to be a film-form image-receiving layer to be laminated over a support; or used alone, without being coated over any support, to constitute an image-receiving member (e.g., film form) (image-receiving layer functional also as its support).
  • an image-receiving member e.g., film form
  • the image-receiving layer formed on a transparent support, may have thereon an opaque layer (reflective layer) containing titanium dioxide dispersed into gelatin.
  • the opaque layer serves to enable the transferred color image to clearly appear as a reflective-type color image when viewed from the transparent support side.
  • the mixture was further mixed with 1.6 ml of a silver halide emulsion containing a red-sensitive silver halide (of a mean particle size of 0.1 wm ) in silver equivalent of 4.8 x 10- 4 moles (also containing 0.12 g of gelatin) to thus prepare a coating liquid.
  • the above-prepared coating liquid was coated over a polyethylene terephthalate support so that the wet thickness thereof is a 30 ⁇ m , whereby a cyan dye donator-containing layer as a first light-sensitive layer was coated.
  • Zero point three gram of a Dp' scavenger having the following structure and 0.16 ml of an aqueous 1 % di-(2-ethyl-hexyl)-2-sulfosuccinic acid solution and 0.2 ml of methanol were mixed, and to the mixture were added 0.5 ml of a one-normal sodium hydroxide solution and 2.5 ml of an aqueous 8% gelatin solution.
  • the thus obtained dispersion liquid was neutralized by use of 5% citric acid, and the whole quantity thereof was made 7 ml by adding water thereto.
  • the dispersion liquid was then mixed with 6 ml of the silver 4-sulfobenzotriazole solution, to which were further added 0.32 g of petriol (3-methylpentane-1,3,5-triol) and 0.16 g of polyethylene glycol (molecular weight 300), and then water was added to the mixture to make the whole quantity thereof 15 ml.
  • the thus obtained coating liquid for the first interlayer was coated over the foregoing first light-sensitive layer (cyan dye donator-containing layer) so that the wet thickness thereof is 15 ⁇ m , thus coating the first interlayer.
  • a coating liquid prepared by dispersing 0.1 g of a yellow dye having the following structure into the above first interlayer's coating liquid was used to be coated over the above magenta dye donator-containing layer so that the wet thickness thereof is 15 ⁇ m, thus forming a second interlayer.
  • a coating liquid of a similar composition to that of the first interlayer's coating liquid except that the 4-sulfobenzotriazole was eliminated therefrom was used to be coated over the above yellow dye donator-containing layer so that the wet thickness thereof is 10 ⁇ m, thus forming a protective layer.
  • the above-obtained heat-development-type color light-sensitive material after being dried, was exposed through an optical step wedge to 1600-C.M.S white light, blue light and green light.
  • the total amount of the binder used in the measured heat-development-type color light-sensitive material sample ls about 5.2 g per m 2 of the support, that of the gelatin used is about 1.7 g, and that of the heat solvent used is about 4.2 g, and the color light-sensitive material sample is a light-sensitive material for this invention.
  • the heat-development-type color light-sensitive material of this invention has not only excellently high maximum densities and low minimum densities but also excellent color separability.
  • Samples were prepared in quite the same manner as in Example 1 except that the total amount and kind of the binder, the amount of the gelatin, and the amount of the heat solvent (the proportion of the amount of the heat solvent to the total amount of the binder is constant: 80% by weight) were changed as shown in Table 2, and then the samples each was exposed and heat-developed in the same manner as in Example 1. The dye image transferred onto the image-receiving paper of each sample was measured in the same manner as in Example 1. The obtained results are as given in the following Table 2.
  • PVP polyvinyl pyrrolidone
  • PVA polyvinyl alcohol
  • Dmax maximum density
  • Dmin minimum density
  • each of the samples (Sample No 1 to 5) for the present invention is capable of producing a transfer dye image having a small fog in the high density and excellent color separability
  • the comparative sample (Sample No 7) that contains a smaller amount of the binder than do the samples of the invention is inferior in the color separability
  • the comparative sample (Sample No. 8) that contains an excessive amount of the binder has an increased fog and is inferior in the transferability of the dye from the bottom layer.
  • each of Samples 9 and 10 which contain heat solvents in the same amount as that used in the sample of Example 1, produces a transfer dye image having excellent heat- transferability, high maximum density with a small fog and satisfactory color-separability, whereas Sample 8, which contains a relatively small amount of heat solvents, produces an image inferior in the transfer density to the above Samples 9 and 10, and if the amount of the heat solvents is increased, although the sample produces an image excellent in the transfer density, its fog also becomes increasing to some extent.

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  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
EP85305952A 1984-08-21 1985-08-21 Heat-developable color light-sensitive material Expired EP0174135B2 (en)

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JP2681641B2 (ja) * 1987-12-17 1997-11-26 コニカ株式会社 熱現像カラー感光材料
JPH0827526B2 (ja) * 1988-03-24 1996-03-21 富士写真フイルム株式会社 熱現像カラー感光材料
DE69030830T2 (de) * 1989-03-09 1997-09-18 Fuji Photo Film Co Ltd Wärmeentwickelbares lichtempfindliches Farbmaterial
JP2631552B2 (ja) * 1989-04-17 1997-07-16 富士写真フイルム株式会社 カラー現像主薬及び画像形成方法
US5147843A (en) * 1991-05-16 1992-09-15 Eastman Kodak Company Polyvinyl alcohol and polyvinyl pyrrolidone mixtures as dye-donor subbing layers for thermal dye transfer
US6277537B1 (en) * 1991-12-06 2001-08-21 Eastman Kodak Company Dye diffusion image separation systems with thermal solvents
DE69422080T2 (de) * 1993-04-14 2000-04-27 Fuji Photo Film Co., Ltd. Lichtempfindliches durch Wärmebehandlung entwickelbares Farbmaterial
JPH0685305U (ja) * 1993-05-21 1994-12-06 清子 利根川 スカートの下着
WO1997004357A2 (en) * 1995-07-18 1997-02-06 Agfa-Gevaert Naamloze Vennootschap Photothermographic recording material
US6790569B2 (en) 2000-06-13 2004-09-14 Eastman Kodak Company Color photothermographic elements comprising phenolic thermal solvents
US6368779B1 (en) * 2000-09-21 2002-04-09 Eastman Kodak Company High speed photothermographic materials and methods of making and using same
US8367288B2 (en) * 2009-04-27 2013-02-05 Canon Kabushiki Kaisha Yellow toner
JP5546156B2 (ja) * 2009-04-27 2014-07-09 キヤノン株式会社 色素化合物、該色素化合物を含有する顔料分散剤、顔料組成物、及び顔料分散体
US8536087B2 (en) 2010-04-08 2013-09-17 International Imaging Materials, Inc. Thermographic imaging element
EP4359219A1 (en) 2021-06-23 2024-05-01 International Imaging Materials Inc. Thermographic imaging element

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JPS57207250A (en) * 1981-06-17 1982-12-18 Fuji Photo Film Co Ltd Heat developing color photosensitive material
JPS5840551A (ja) * 1981-09-02 1983-03-09 Fuji Photo Film Co Ltd カラ−画像形成方法
JPS5858543A (ja) * 1981-10-02 1983-04-07 Fuji Photo Film Co Ltd 熱現像カラ−感光材料およびそれを用いたカラ−画像形成方法
CH653780A5 (fr) * 1981-11-12 1986-01-15 Eastman Kodak Co Produit pour la photographie par transfert d'image.
US4478929A (en) * 1982-09-30 1984-10-23 Eastman Kodak Company Dye image transfer film unit with tabular silver halide
US4426441A (en) * 1982-12-03 1984-01-17 Eastman Kodak Company Dye-forming developers in an imaging material and process
JPS59188644A (ja) * 1983-04-09 1984-10-26 Fuji Photo Film Co Ltd 画像形成方法
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EP0174135A3 (en) 1987-05-20
JPS6152643A (ja) 1986-03-15
EP0174135B1 (en) 1989-04-26
JPH0257298B2 (enrdf_load_stackoverflow) 1990-12-04
DE3569838D1 (en) 1989-06-01
US4770981A (en) 1988-09-13

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